Synergistic Formulation Including At Least One Gibberellin Compound and Salicyclic Acid

ABSTRACT

A synergistic formulation comprising at least one gibberellin (GA) compound and salicylic acid (SA) for delaying fruit ripening and maintaining good quality of fruit under storage.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a continuation application of U.S. Ser. No. 16/399,546 filedApr. 30, 2019, the entire contents of which is incorporated herein byreference. This application claims the benefit, under 35 U.S.C. 119(e),of U.S. Provisional Application No. 62/664,867 filed Apr. 30, 2018, thecontents of which are incorporated herein by reference.

BACKGROUND OF THE INVENTION Field of the Invention

The present invention is a synergistic formulation including at leastone gibberellin compound and salicyclic acid. This synergisticformulation delays fruit ripening and maintains good quality of fruitunder storage. Additional beneficial fruit quality parameters achievedby using the synergistic formulation include fruit firmness, color anddecrease in postharvest diseases.

Description of Related Art

Harvested fruits are classified as climacteric and non-climacteric basedon their rate of respiration, which is proportional to the rate of fruitdecay. Respiration is the process that provides energy to all organisms.Respiration consists of the degradation of stored organic materials suchas proteins, fats and carbohydrates into simple end products with arelease of energy. Oxygen is consumed in the process and carbon dioxideCO₂ is produced.

Examples of climacteric fruits include, but are not limited to, apple,apricot, avocado, bananas, biriba, blueberry, breadfruit, cherimoya,durian, fijoa, fig, guava, jackfruit, kiwifruit, mango, mangosteen,muskmelon, nectarine, papaya, passion fruit, peach, pear, persimmon,plantain, plum, quince, rambutan, sapodilla, sapote, soursop, sweetsop,and tomato.

Examples of non-climacteric fruits include, but are not limited to,blackberry, cacao, carambola, cashew apple, cherry, cranberry, cucumber,date, eggplant, grape, grapefruit, jujube, lemon, lime, longan, loquat,lychee, okra, olive, orange, pea, pepper, pineapple, pomegranate,prickly pear, raspberry, strawberry, summer squash, tamarillo, tangerineand mandarine and watermelon.

From the group of climacteric fruits, banana is the 2^(nd) largest fruitcrop in the world and are cultivated in more than 120 countries intropical and subtropical areas. The main regions of the world thatexport bananas are Latin America, the Caribbean, Asia, and Africa, andthe major importers of bananas are the European Union and United States.Bananas need to be harvested at physiological maturity and then shippedoverseas for 30 to 40 days under low temperatures (13.2° C./52° F.) toreduce their metabolism, ethylene production, and the ripening process.Sometimes bananas are placed in modified or controlled atmosphere roomswith ethylene absorbers such as potassium permanganate to inhibitethylene production.

Gibberellic acid (GA₃) is a plant growth regulator commonly used toensure that bananas remain un-ripened during shipment. GA₃ has beenshown to delay loss in fruit firmness and vitamin C content, and delayfruit ripening, senescence and retard peel chlorophyll degradation injujube. It has also been tested in mangoes and delays loss in totalweight, chlorophyll, and ascorbic acid content and reduces amylase andperoxidase activity. GA₃ can initiate re-greening in citrus fruits anddelays the appearance of red color in tomatoes. Moreover, GA₃ appliedexogenously on banana slices does not alter respiration rate or ethyleneprofile, but postpones by 2 days the accumulation of sucrose. While GA₃allows bananas to stay unripe, in some cases it causes them to soften,which is undesirable to consumers.

Salicylic acid (SA), a plant phenolic compound and a plant defensehormone, has also been shown to slow down banana ripening. Bananastreated with SA at either 0.5 mM or 1 mM had firmer fruits, lower sugarcontent, and a decrease in respiration rates. Salicylic acid inhibitoryeffects on ethylene biosynthesis have been known since the late 80's incarrot and pear cell suspension culture studies where the use of SAreduced ethylene production and allowed proliferation of the cellculture. Acetyl salicylic acid has been shown to inhibit ethyleneproduction in apples. It has also been proven that SA inhibits cell walland membrane degrading enzymes (polygalacturonase, lipoxygenase,cellulose and pectin methylesterase) and as a result of this inhibition,banana fruits treated with SA are firmer.

Later studies on tomato fruit ripening have evaluated the use of eitherGA₃, salicylic acid, or calcium chloride (for its role on cell wallrigidity) in slowing ripening. Of all treatments tested, GA₃ at 0.1%,CaCl₂ at 1.5% or SA at 0.4 mM extended the shelf life of tomatoes.Similar studies conducted in Cavendish bananas tested varyingconcentrations of either GA or SA and determined that 300 ppm GA₃ or 4mM SA caused a more considerable delay in ripening than othertreatments.

BRIEF SUMMARY OF THE INVENTION

A synergistic formulation comprising at least one gibberellin compound(GA) and salicylic acid (SA) reduces the production of ethylene whilemaintaining the firmness and color of an agricultural product, whichallows for a longer shelf life.

BRIEF DESCRIPTION OF THE DRAWING(S)

The features and advantages of the present invention will becomeapparent from the following detailed description of a preferredembodiment thereof, taken in conjunction with the accompanying drawings,in which:

FIG. 1 is a graph showing the fruit firmness at 7 days after treatmentwith a control (CT), salicylic acid (SA) alone, gibberellic acid (GA)alone, and the GA+SA synergistic formulation of the present invention;

FIG. 2 is a graph showing the fruit firmness at 10 days after treatmentwith a control (CT), salicylic acid (SA) alone, gibberellic acid (GA)alone, and the GA+SA synergistic formulation of the present invention;

FIG. 3 is a graph showing the ethylene emission at 7 days aftertreatment with a control (CT), salicylic acid (SA) alone, gibberellicacid (GA) alone, and the GA+SA synergistic formulation of the presentinvention;

FIG. 4 is a graph showing the ethylene emission at 10 days aftertreatment with a control (CT), salicylic acid (SA) alone, gibberellicacid (GA) alone, and the GA+SA synergistic formulation of the presentinvention;

FIG. 5 is a graph showing the ethylene emission in Cavendish bananas at21 days after treatment, this simulates the overseas transport at 13.5°C. The banana fruits were subjected to a control (CT), gibberellic acid(GA) alone, salicylic acid (SA) alone and the GA+SA synergisticformulation of the present invention;

FIG. 6 is a graph showing the fruit firmness of Cavendish bananas 6 daysafter force ripening (treated with 100 ppm of ethylene simulatingcommercial handling of bananas). The bananas were subjected to a control(CT), gibberellic acid (GA) alone, salicylic acid (SA) alone and theGA+SA synergistic formulation of the present invention;

FIG. 7 is a graph showing the peel color of Cavendish bananas 6 daysafter force ripening (treated with 100 ppm of ethylene simulatingcommercial handling of bananas). The bananas were subjected to a control(CT), gibberellic acid (GA) alone, salicylic acid (SA) alone and theGA+SA synergistic formulation of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

The synergistic formulation comprises, optionally consists essentiallyof, or optionally consists of, at least one gibberellin (GA) compound;salicylic acid (SA); optionally at least one solvent; optionally atleast one additional component that does not affect the ethyleneproduction of the present synergistic formulation, optionally at leastone non-ionic or anionic surfactants; and optionally at least onecustomary adjuvants, wherein said synergistic formulation reducingethylene production in agricultural products, and preferably reducescolor change of the agricultural product. In one embodiment, thesynergistic formulation comprises, optionally consisting essentially of,or optionally consisting of, at least one gibberellin compound andsalicylic acid as the only active agents that assist in reducingethylene production in agricultural products. In another embodiment, thesynergistic formulation comprises, optionally consisting essentially of,or optionally consisting of, at least one gibberellin compound andsalicylic acid as the only active agents that trigger a positivephysiological response in agricultural products. In another embodiment,the synergistic formulation comprises, optionally consists essentiallyof, or optionally consists of, at least one gibberellin (GA) compoundand salicylic acid (SA) without the addition of any halogenatedcompound, such as chlorinated compounds, for example CaCl₂.

“Active agents” are generally understood to include those compounds thatassist in reducing ethylene production in agricultural products.Additionally, “active agents” are any compounds that trigger a positivephysiological response in agricultural products.

Salicylic acid is general known to have the following chemicalstructure:

Gibberellin compounds are generally understood to be tetracyclicditerpene acids. In one embodiment of the present invention, the atleast one gibberellin compound is selected from the group consisting ofgibberellic acid (“GA₃”), gibberellin₄ (“GA₄”), gibberellin_(4/7)(“GA_(4/7)”) and combinations thereof. In a preferred embodiment of thepresent invention, the at least one gibberellin compound is gibberellicacid (GA₃) having the following structure:

In one embodiment of the present invention, the synergistic formulationincludes GA: SA in a ratio of 20:1 to 1:1, or 10:1 to 1:1, 5:1 to 2:1,or 3:1 to 2:1. In one embodiment, the synergistic formulation includesat least one solvent with 20-2000 ppm GA, or 100-1800 ppm GA, or200-1500 ppm GA, or 500-1500 ppm GA; and 20-2000 ppm salicylic acid(SA), or 50-1000 ppm SA, or 50-800 ppm SA. In another embodiment, thesynergistic formulation includes at least one solvent with 625-1250 ppmGA and 62.5-625 ppm SA.

In one embodiment of the present invention, the synergistic formulationcomprises, optionally consists essentially of, or optionally consistsof, up to 20 wt. % at least one gibberellin (GA) compound based on thetotal weight of the formulation; up to at least 25 wt. % salicylic acid(SA) based on the total weight of the formulation; optionally at least50 wt. % at least one solvent, preferably propylene glycol and/or PEG,based on the total weight of the formulation; optionally at least oneadditional component that does not affect the ethylene production of thepresent synergistic formulation, optionally at least one non-ionic oranionic surfactants; and optionally at least one customary adjuvants,wherein said synergistic formulation reducing ethylene production inagricultural products.

In alternate embodiments, the synergistic formulation includes 5-20 wt.% at least one gibberellin compound, or optionally 10-20 wt. % at leastone gibberellin compound, or optionally 10-15 wt. % at least onegibberellin compound, or optionally 10-12 wt. % at least one gibberellincompound based on the total weight of the formulation. In alternateembodiments, the synergistic formulation may include the previouslylisted amounts of GA compound and 0.5-25 wt. % salicylic acid, oroptionally 4-25 wt. % salicyclic acid, or optionally 4-20 wt. %salicyclic acid, or optionally 4-10 wt. % salicyclic acid, or optionally4-5 wt. % salicyclic acid based on the total weight of the formulation.

In one embodiment, the synergistic formulation comprises, optionallyconsists essentially of, or optionally consists of, 18-20 wt. % of atleast one gibberellin (GA) compound based on the total weight of theformulation; 20-25 wt. % salicylic acid (SA) based on the total weightof the formulation; 50-62 wt. % at least one solvent, preferablypropylene glycol and/or PEG, based on the total weight of theformulation; optionally at least one additional component that does notaffect the ethylene production of the present synergistic formulation,optionally at least one non-ionic or anionic surfactants; and optionallyat least one customary adjuvants, wherein said synergistic formulationreducing ethylene production in agricultural products.

In one embodiment, the synergistic formulation comprises, optionallyconsists essentially of, or optionally consists of, 8-10 wt. % of atleast one gibberellin (GA) compound based on the total weight of theformulation; 8-10 wt. % salicylic acid (SA) based on the total weight ofthe formulation; 75-84 wt % at least one solvent, preferably propyleneglycol and/or PEG, based on the total weight of the formulation;optionally at least one additional component that does not affect theethylene production of the present synergistic formulation, optionallyat least one non-ionic or anionic surfactants; and optionally at leastone customary adjuvants, wherein said synergistic formulation reducingethylene production in agricultural products.

In one embodiment, the synergistic formulation comprises, optionallyconsists essentially of, or optionally consists of, 18-20 wt. % of atleast one gibberellin (GA) compound based on the total weight of theformulation; 0.5-1 wt. % salicylic acid (SA) based on the total weightof the formulation; 75-81.5 wt. % at least one solvent, preferablypropylene glycol and/or PEG, based on the total weight of theformulation; optionally at least one additional component that does notaffect the ethylene production of the present synergistic formulation,optionally at least one non-ionic or anionic surfactants; and optionallyat least one customary adjuvants, wherein said synergistic formulationreducing ethylene production in agricultural products.

In one embodiment, the synergistic formulation comprises, optionallyconsists essentially of, or optionally consists of, about 12 wt. % of atleast one gibberellin (GA) compound based on the total weight of theformulation; about 4.5 wt. % salicylic acid (SA) based on the totalweight of the formulation; 80-83.5 wt. % at least one solvent,preferably propylene glycol and/or PEG, based on the total weight of theformulation; optionally at least one additional component that does notaffect the ethylene production of the present synergistic formulation,optionally at least one non-ionic or anionic surfactants; and optionallyat least one customary adjuvants, wherein said synergistic formulationreducing ethylene production in agricultural products.

In one embodiment of the present invention, the synergistic solution isprovided as a non-aqueous solution. As provided herein, it is understoodthat the term “non-aqueous” may include small amounts of water,preferably less than 5 wt. %, preferably less than 4 wt. %, preferablyless than 3 wt. %, preferably less than 2 wt. %, preferably less than 1wt. %, and preferably less than 0.5 wt. % based on the total weight ofthe synergistic formulation. However, it is preferred that water is notintentionally added to the present synergistic formulation.

The synergistic formulation of the present invention preferably includesat least one solvent such that the total amount of solvents present is≥50 wt. %, ≥60 wt. %, ≥70 wt. %, ≥80 wt. %, or ≥85 wt. %, or ≥90 wt. %,or ≥95 wt. %, or ≥99 wt. % based on the total weight of the synergisticformulation.

In one embodiment of the present invention, the synergistic formulationincludes the above-identified amounts of SA and GA and at least onesolvent selected from a wide variety of organic solvents. Such solventsinclude, but are not limited to, ethanol, n-propanol, iso-propanol,ethyl lactate, 3-hydroxybutyrate (ethyl and propyl esters), polymericand non-polymeric glycols, glycerols, polyethylene glycol, polypropyleneglycol, propylene carbonate and combinations thereof. In one embodiment,propylene glycol is used as the solvent in the synergistic formulationof the present invention. Preferably, the synergistic formulationincludes the above-identified amounts of SA and GA and ≥50 wt. %propylene glycol, or ≥60 wt. % propylene glycol, or ≥70 wt. % propyleneglycol, ≥80 wt. % propylene glycol, or ≥85 wt. % propylene glycol, or≥90 wt. % propylene glycol, or ≥95 wt. % propylene glycol, or ≥99 wt. %propylene glycol based on the total weight of the synergisticformulation. In another embodiment, at least one polyethylene glycol(PEG) with a molecular weight from 190-420 is used as the solvent in thesynergistic formulation of the present invention. Preferably, thesynergistic formulation includes the above-identified amounts of SA andGA and ≥50 wt. % polyethylene glycol, or ≥60 wt. % polyethylene glycol,or ≥70 wt. % polyethylene glycol ≥80 wt. % polyethylene glycol, or ≥85wt. % polyethylene glycol, or ≥90 wt. % polyethylene glycol, or ≥95 wt.% polyethylene glycol, or ≥99 wt. % polyethylene glycol based on thetotal weight of the synergistic formulation. Preferably, the synergisticformulation includes the above-identified amounts of SA and GA and ≥50wt. % of a combination of solvents, such as polyethylene glycol andpropylene glycol, or ≥60 wt. % of a combination of solvents, such aspolyethylene glycol and propylene glycol, or ≥70 wt. % of a combinationof solvents, such as polyethylene glycol and propylene glycol, ≥80 wt. %of a combination of solvents, such as polyethylene glycol and propyleneglycol, or ≥85 wt. % of a combination of solvents, such as polyethyleneglycol and propylene glycol, or ≥90 wt. % of a combination of solvents,such as polyethylene glycol and propylene glycol, or ≥95 wt. % of acombination of solvents, such as polyethylene glycol and propyleneglycol, or ≥99 wt. % of a combination of solvents, such as polyethyleneglycol and propylene glycol based on the total weight of the synergisticformulation.

In one embodiment of the present invention, the synergistic formulationincludes polar and semi-polar organic solvent is a single or combinationof “non-volatile, polar or semi-polar organic solvents”, herein definedto exclude those volatile organic compounds (VOCs) with a vapor pressureless than 0.1 mm Hg at 20° C. A polar solvent is defined as that whichdissolves ionic and other polar solutes. Semi-polar solvents induce acertain degree of polarity in non-polar molecules. A measurement ofpolarity may be determined by its dielectric constant. Semi- and polarsolvents defined in this invention are those solvents that havedielectric constants greater than 10 @ 20° C. For example, thesynergistic formulation may include, but is not limited to the followingsolvents: alcohols, dialkyl ketones, alkylene carbonates, alkyl esters,pyrrolidones, aryl esters, and combinations thereof.

The synergistic formulation may also include non-ionic or anionicsurfactants including, but not limited to the group consisting ofcarboxylates, sulfonates, natural oils, alkylamides, arylamides,alkylphenols, arylphenols, ethoxylated alcohols, polyoxygethylene,carboxylic esters, polyalkylglycol esters, anhydrosorbitols, glycolesters, carboxylic amides, monoalkanolamine, poloxyethylene fatty acidamides, polysorbates, cyclodextrins, sugar based, silicone based,polyalkylated alcohols, alkylaryl ethoxylates, and combinations thereof.In one embodiment, the synergistic formulation includes theabove-identified amounts of SA and GA and optional solvents and a totalamount of surfactants of ≤10 wt. %, or ≤5 wt. %, or ≤1 wt. % based onthe total weight of the synergistic formulation.

The synergistic formulation may include the above-identified amounts ofGA compound, SA, optional solvents, optional surfactants and optionaladditional components such that the total amounts of all such additionalcomponents is preferably less than 10 wt. %, or less than 5 wt. %, orless than 1 wt. % based on the total weight of the synergisticformulation. Preferably, such components do not affect the ethyleneproduction of the present synergistic formulation. These additionalcomponents include surface active agents, crystal growth inhibitors,fungicides, stickers, spreaders, leaf penetrants, dispersants, systemicacquired resistance inducers, systemic acquired resistance inhibiters,anti-foaming agents, preservatives, pH regulators, cosolvents,humectants, dyes, UV protectants, vehicles, sequestrants, andcombinations thereof, or other components which do not affect theethylene production of the present synergistic formulation.

In one embodiment of the present invention, the synergistic formulationis prepared by combining the above-identified amounts of GA compound,SA, optional solvents, optional surfactants and optional additionalcomponents with optional customary adjuvants. In one embodiment of thepresent invention the total amounts of all such customary adjuvants ispreferably less than 10 wt. %, or less than 5 wt. %, or less than 1 wt.% based on the total weight of the synergistic formulation.

The synergistic formulation may be provided in the form of solutions,emulsions, suspensions, pastes, powders or granulates. In a preferredembodiment, the synergistic formulation is a solution, most preferably anon-aqueous solution.

The active agents are used in the form of their formulations or theforms of application prepared therefrom or their mixtures with furthercomponents in customary manner, e.g. by means of pouring, splashing,spraying or dusting. Suitable forms of application are, for example,aqueous or non-aqueous solutions, which are stabilized with customarydispersing agents, suspensions, emulsions, spray agents or dustingagents. Other forms of application involved the immersion of commodityor agricultural product into a solution containing the active agents.Application could be done pre-harvest and post-harvest.

The synergistic formulation of the present invention may be used on anyagricultural product, for example, on: bananas, apples, mangoes,avocados, artichokes, blueberries, carrots, celery, cherries, citrus,collard greens, broccoli, cucumbers, corn, grapes, melons, pecans,peppers, pineapples, rice, rhubarb, spinach, stone fruits, strawberries,watercress and other plants in need of treatment. In one preferredembodiment, the synergistic formulation is used on bananas to reduceethylene production while maintaining firmness to yield a fruit with alonger shelf life.

It should be understood that the recitation of a range of valuesincludes all of the specific values in between the highest and lowestvalue. For example, the recitation of “20-2000 ppm” includes all of thevalues between 20 to 2000 such that either the upper or lower limits mayinclude, but are not limited to 30, 30, 40, 50, 60, 70, 80, 90, 100,200, 300, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400,1500, 1600, 1700, 1800, and 1900 ppm. For example, the recitation of“10:1 to 1:1”” includes all of the values between 10:1 to 1:1 such thateither the upper or lower limits may include, but are not limited to,9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1 to 1:1. For example, therecitation of “up to 20 wt. %” includes all of the values between0.001-20 such that either the upper or lower limits may include, but arenot limited to 0.001, 0.01, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9,1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and20. For example the recitation of “up to at least 25 wt. %” includes allof the values between 0.001-25 such that either the upper or lowerlimits may include, but are not limited to 0.001, 0.01, 0.1, 0.2, 0.3,0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13,14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 and 25. For example, therecitation of “at least 50 wt. %” includes all of the values between50-100 such that either the upper or lower limits may include, but arenot limited to 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63,64. 65, 66, 67, 68, 69 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81,82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99,and 100.

As used herein, all numerical values relating to amounts, weightpercentages and the like are defined as “about” or “approximately” eachparticular value, namely, plus or minus 10% (+−10%). For example, thephrase “at least 5% by weight” is to be understood as “at least 4.5% to5.5% by weight.” Therefore, amounts within 10% of the claimed values areencompassed by the scope of the claims. The percentages of thecomponents in the formulations are listed by weight percentage based onthe total weight of the formulation, unless stated otherwise.

A basic and novel characteristic of the present invention is that thesynergistic formulation comprises, optionally consists essentially or,or optional consists of, at least one gibberellin compound (GA) andsalicylic acid (SA), optionally in solution, that reduces the productionof ethylene while maintaining the firmness and color of an agriculturalproduct, which allows for a longer shelf life.

The following example illustrates one embodiment of the presentinvention. Those of skill in the art would understand how to modify theexample to arrive at the present invention.

Example 1

The active agents gibberellic acid (GA₃) and salicylic acid (SA) weretested separately and mixed together (GA+SA synergistic formulation) todetermine their effects on Thailand banana shelf life. Ethylene emissionand fruit hardness/fruit firmness were the parameters measured in thistest.

The active agents were tested at full rate when used alone and at halfrate when combined in the synergistic formulation. Initial experiments,not reported here, were done to determine the best dose combination ofactive agents.

Treatments consisted of a Control-water treatment, SA 552 ppm (4 mM) inpropylene glycol, GA₃ 1500 ppm in propylene glycol, and GA₃ 750 ppm (12wt. %)+SA 276 ppm (4.5 wt. %) (2 mM) in propylene glycol. Theseformulations including the active agents were dissolved in water andthen 5 ml were sprayed over each banana. The bananas were air dried for25 minutes and then placed in transparent closed boxes at 75° F. for upto 10 days.

Ethylene was measured with a Portable Ethylene Analyzer F-900, FelixInstruments. The fruits were placed for 40-60 minutes in sealedcontainers adapted with septum stoppers and then a syringe was used tosample the air in the headspace. Ethylene was determined in ppm/g/minunits. The fruit hardness/fruit firmness was measured in Newtons (forceunits) for a 4 mm depth with a Texture analyzer CT-3, 4500 g, BrookFieldAmetek with a TA10 probe.

FIGS. 1-4 show the test results indicating that ethylene emission wasthe lowest when the synergistic formulation was applied to the bananas.And accordingly, the fruit firmness at 10 DAT was the highest when thebananas were treated with the synergistic formulation. This demonstratesthat the synergistic formulation has a stronger effect on fruit ripeningand extending banana shelf life than the individual active agent'sformulations.

A statistical analysis of the data confirms that the synergisticformulation provides significant results as follows:

TABLE 1 7 Day Firmness SA 552 GA₃ 1500 GA₃ 750 + SA 276 P value vscontrol 0.17602 0.68073 0.73437 P value vs SA 552 0.1225 0.39234 P valuevs GA 1500 0.49524

TABLE 2 10 Day Firmness SA 552 GA₃ 1500 GA₃ 750 + SA 276 P value vscontrol 0.76078 0.70965 0.09455 P value vs SA 552 0.46565 0.14888 Pvalue vs GA 1500 0.01981

TABLE 3 7 Day Ethylene Study SA 552 GA₃ 1500 GA₃ 750 + SA 276 P value vscontrol 0.98635 0.05908 0.0013706 P value vs SA 552 0.05558 0.001017097P value vs GA 1500 0.000347125

TABLE 4 10 Day Ethylene Study SA 552 GA₃ 1500 GA₃ 750 + SA 276 P valuevs control 0.29322 0.63964 0.00648 P value vs SA 552 0.04572 8.8E−05 Pvalue vs GA 1500 7.9E−05

Example 2

The active agents Gibberellic acid (GA₃) and Salicylic acid (SA) weretested separately and mixed together (GA+SA synergistic formulation) todetermine their effects on Cavendish banana (most popular commercialbanana) shelf life. Ethylene emission, fruit hardness/fruit firmness andcolor were the parameters measured in this test.

The active agents were tested at full rate when used alone and atdifferent ratios (GA:SA) when combined in the synergistic formulation:˜20:1, ˜10:1, ˜5:1, ˜2.7:1 and ˜1:1.

Treatments consisted of a Control-water treatment, SA 1500 ppm inpropylene glycol , GA₃ 1500 ppm in propylene glycol, and GA₃ 1250 ppm(18.2 wt. %)+SA 62.5 ppm (0.9 wt. %) (˜20:1) in propylene glycol, GA₃1250 ppm (18.2 wt. %)+SA 125 ppm (1.8 wt. %) (˜10:1) in propyleneglycol, GA₃ 1250 ppm (16.7 wt. %)+SA 250 ppm (3.3 wt. %) (˜5:1) inpropylene glycol, GA₃ 750 ppm (12 wt. %)+SA 276 ppm (4.5 wt. %) (˜2.7:1)in propylene glycol and GA₃ 625 ppm (5 wt. %)+SA 625 ppm (5 wt. %)(˜1:1) in propylene glycol. The formulations including the active agentswere dissolved in water and mixed with thiabendazole and imidazole (300ppm each), fungicides used commercially in bananas. Sprays were directedto the crown. The bananas were air dried and then packed in commercialcardboard boxes using an internal plastic liner with 4 holes at thebottom. Packaged fruit was stored in a cold room at 13.5° C. fortransport simulation of 21 days. After transport simulation, the fruitwas transferred to a ripening room at 18° C. for 24 hours and thenethylene at 100-150 ppm was applied for 24 hours using a continuousdischarge catalytic generator (American ripener arco 1200).

Ethylene was measured with a gas chromatograph, (Agilent 7920 FID/TCD).The fruits (950-1500 grams) were placed for 2 hours in sealed containers(2.5 gallons) adapted with septum stoppers and then a syringe was usedto sample the air in the headspace. Ethylene was determined in uL/Kg.hunits. The fruit hardness/fruit firmness was measured in Newtons (forceunits) with a Chatillon DPPH100, conical probe of 5 mm for a fixed depthof 0.5 inch. Peel color was measured with an iWAVE WR10 Colorimeter,which is similar to the CR300 Chroma meter Minolta. Hue values werecalculated based on the a, b and L values read by the device.

FIGS. 5-7 show the test results indicating that ethylene emission rightafter transport simulation, when the bananas are still green, was thelowest when the synergistic formulation of 2.7:1 was applied to thebananas. The fruit firmness and color were measured on bananas that wereexposed to ethylene to induce ripening (force ripening using 100-150 ppmof ethylene), this will show how effective was the postharvest treatmenton banana shelf life. The Hue value for the control is the lowest andall treated bananas have a higher Hue value. The yellow color isequivalent to a Hue value of 90 and green color is equivalent to a Huevalue of 180. The higher the hue the greener the banana peel.

Although the present invention has been disclosed in terms of apreferred embodiment, it will be understood that numerous additionalmodifications and variations could be made thereto without departingfrom the scope of the invention as defined by the following claims:

We claim:
 1. A synergistic formulation comprising, at least onegibberellin (GA) compound; at least 0.00625 wt. % salicylic acid (SA);≥50 wt. % at least one organic solvent; less than 5 wt. % water;optionally at least one non-ionic or anionic surfactants; and optionallyat least one adjuvant, wherein said formulation includes more GA than SAbased on the total weight of the formulation.
 2. The synergisticformulation of claim 1 comprising, up to 20 wt. % of said at least onegibberellin (GA) compound, and 0.00625 to 19 wt. % salicylic acid (SA).3. The synergistic formulation of claim 1 comprising, 18-20 wt. % ofsaid at least one gibberellin (GA) compound; and 50-62 wt. % of said atleast one organic solvent based on the total weight of the formulation.4. The synergistic formulation of claim 1 comprising, 5-18.2 wt. % ofsaid at least one gibberellin (GA) compound; 0.9-5 salicylic acid (SA);and 75-84 wt. % of said at least one organic solvent based on the totalweight of the formulation.
 5. The synergistic formulation of claim 1comprising, 18-20 wt. % of said at least one gibberellin (GA) compound;0.5-1 wt. % salicylic acid (SA); and 75-81.5 wt. % of said at least oneorganic solvent based on the total weight of the formulation.
 6. Thesynergistic formulation of claim 1 comprising, about 12 wt. % of said atleast one gibberellin (GA) compound; about 4.5 wt. % salicylic acid(SA); and 80-83 wt. % of said at least one organic solvent based on thetotal weight of the formulation.
 7. The synergistic formulation of claim1 wherein said at least one gibberellin compound and said salicylic acidare the only active agents in said formulation.
 8. The synergisticformulation of claim 1 wherein no halogenated compounds are present insaid formulation.
 9. The synergistic formulation of claim 8 wherein noCaCl₂ is present in said formulation.
 10. The synergistic formulation ofclaim 1, wherein said gibberellin compound is selected from the groupconsisting of gibberellic acid (“GA₃”), gibberellin₄ (“GA₄”),gibberellin4/7 (“GA_(4/7)”), and combinations thereof.
 11. Thesynergistic formulation of claim 10 wherein said gibberellin compound isgibberellic acid (“GA₃”).
 12. The synergistic formulation of claim 1,wherein said at least one organic solvent is selected from the groupconsisting of alcohols, dialkyl ketones, alkylene carbonates, alkylesters, pyrrolidones, aryl esters, and combinations thereof.
 13. Thesynergistic formulation of claim 1, wherein said at least one organicsolvent is selected from the group consisting of ethanol, n-propanol,iso-propanol, ethyl lactate, 3-hydroxybutyrate (ethyl and propylesters), polymeric and non-polymeric glycols, glycerols, polyethyleneglycol, polypropylene glycol, propylene carbonate and combinationsthereof.
 14. The synergistic formulation of claim 1, wherein said atleast one organic solvent is propylene glycol.
 15. The synergisticformulation of claim 1, wherein said at least one organic solvent is atleast one polyethylene glycol (PEG) with a molecular weight from190-420.
 16. The synergistic formulation of claim 1 comprising ≤10 wt. %of said at least one non-ionic or anionic surfactants based on the totalweight of the formulation.
 17. The synergistic formulation of claims 1comprising less than 10 wt. % of said at least one adjuvant based on thetotal weight of the synergistic formulation.
 18. A synergisticformulation consisting essentially of, up to 20 wt. % at least onegibberellin (GA) compound based on the total weight of the formulation;0.00625 to 19 wt. % salicylic acid (SA) based on the total weight of theformulation; at least 50 wt. % at least one organic solvent based on thetotal weight of the formulation; less than 5 wt. % water based on thetotal weight of the formulation; less than 10 wt. % at least oneadditional component; ≤10 wt. % at least one non-ionic or anionicsurfactants based on the total weight of the formulation; ≤10 wt. % atleast one adjuvant based on the total weight of the formulation, whereinsaid formulation includes more GA than SA based on the total weight ofthe formulation.
 19. A synergistic formulation consisting of, up to 20wt. % at least one gibberellin (GA) compound based on the total weightof the formulation; 0.00625 to 19 wt. % salicylic acid (SA) based on thetotal weight of the formulation; at least 50 wt. % at least one organicsolvent based on the total weight of the formulation; less than 5 wt. %water based on the total weight of the formulation; less than 10 wt. %at least one additional component selected from the group consisting ofsurface active agents, crystal growth inhibitors, fungicides, stickers,spreaders, leaf penetrants, dispersants, systemic acquired resistanceinducers, systemic acquired resistance inhibiters, anti-foaming agents,preservatives, pH regulators, cosolvents, humectants, dyes, UVprotectants, vehicles, sequestrants, and combinations thereof, ≤10 wt. %at least one non-ionic or anionic surfactants based on the total weightof the formulation; ≤10 wt. % at least one adjuvant based on the totalweight of the formulation wherein said formulation includes more GA thanSA based on the total weight of the formulation.